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Switchable hydrophilicity solvents (SHSs) are solvents defined by their ability to switch from their hydrophobic form to a hydrophilic form when brought into contact with an acidic trigger such as CO2.

Flow transport in confined spaces is ubiquitous in technological processes, ranging from separation and purification of pharmaceutical ingredients by microporous membranes and drug delivery in biomedical treatment to chemical and biomass conversion in catalyst-packed reactors and carbon dioxide sequestration. In this work, we suggest a distinct pathway for enhanced liquid transport in a confined space via propelling microdroplets. These microdroplets can form spontaneously from localized liquid-liquid phase separation as a ternary mixture is diluted by a diffusing poor solvent. High speed images reveal how the microdroplets grow, break up and propel rapidly along the solid surface, with a maximal velocity up to ∼160 μm s-1, in response to a sharp concentration gradient resulting from phase separation. The microdroplet propulsion induces a replenishing flow between the walls of the confined space towards the location of phase separation, which in turn drives the mixture out of equilibrium and leads to a repeating cascade of events. Our findings on the complex and rich phenomena of propelling droplets suggest an effective approach to enhanced flow motion of multicomponent liquid mixtures within confined spaces for time effective separation and smart transport processes. This journal is

We present a curious effect observed during the dissolution process of water-immersed long-chain alcohol drops with an entrapped air bubble. These droplets dissolve while entrapping an air bubble pinned at the substrate. We qualitatively describe and explain four different phases that are found during the dissolution of this kind of system. The dissolution rate in the four phases differ dramatically. When the drop-water interface and the air bubble contact each other, rapid cyclic changes of the morphology are found: The breakage of the thin alcohol layer in between the bubble and the water leads to the formation of a three phase contact line. If the surface tension of the water-air interface supersedes those of the alcohol-water and alcohol-air interfaces, alcohol from the droplet is pulled upwards, leading to a closure of the air-water interface and the formation of a new thin alcohol film, which then dissolves again, leading to a repetition of the series of events. We call this sequence of events Marangoni puffing. This only happen for alcohols of appropriate surface tension. The Marangoni puffing is an intermediate state. In the final dissolution phases the Marangoni forces dramatically accelerate the dissolution rate, which then becomes one order of magnitude faster than the purely buoyancy-convective driven dissolution. Our results have bearing on various dissolution processes in multicomponent droplet systems.

Surface nanobubbles are nanoscopic spherical-cap shaped gaseous domains on immersed substrates which are stable, even for days. After the stability of a {\it single} surface nanobubble has been theoretically explained, i.e. contact line pinning and gas oversaturation are required to stabilize them against diffusive dissolution [Lohse and Zhang, Phys.\ Rev.\ E 91, 031003 (R) (2015)], here we focus on the {\it collective} diffusive interaction of {\it multiple} nanobubbles. For that purpose we develop a finite difference scheme for the diffusion equation with the appropriate boundary conditions and with the immersed boundary method used to represent the growing or shrinking bubbles. After validation of the scheme against the exact results of Epstein and Plesset for a bulk bubble [J. Chem. Phys. 18, 1505 (1950)] and of Lohse and Zhang for a surface bubble, the framework of these simulations is used to describe the coarsening process of competitively growing nanobubbles. The coarsening process for such diffusively interacting nanobubbles slows down with advancing time and thus increasing bubble distance. The present results for surface nanobubbles are also applicable for immersed surface nanodroplets, for which better controlled experimental results of the coarsening process exist.

Evaporation of multi-component drops is crucial to various technologies and has numerous potential applications because of its ubiquity in nature. Superamphiphobic surfaces, which are both superhydrophobic and superoleophobic, can give a low wettability not only for water drops but also for oil drops. In this paper, we experimentally, numerically and theoretically investigate the evaporation process of millimetric sessile ouzo drops (a transparent mixture of water, ethanol, and trans-anethole) with low wettability on a superamphiphobic surface. The evaporation-triggered ouzo effect, i.e. the spontaneous emulsification of oil microdroplets below a specific ethanol concentration, preferentially occurs at the apex of the drop due to the evaporation flux distribution and volatility difference between water and ethanol. This observation is also reproduced by numerical simulations. The volume decrease of the ouzo drop is characterized by two distinct slopes. The initial steep slope is dominantly caused by the evaporation of ethanol, followed by the slower evaporation of water. At later stages, thanks to Marangoni forces the oil wraps around the drop and an oil shell forms. We propose an approximate diffusion model for the drying characteristics, which predicts the evaporation of the drops in agreement with experiment and numerical simulation results. This work provides an advanced understanding of the evaporation process of ouzo (multi-component) drops., 41 pages, 8 figures

In the process of solvent exchange, oil droplets nucleate and grow on a solid substrate in response to the oversaturation generated through the displacement of a good oil solvent by a poor one. The mean size of the droplets depends on flow rate, flow geometry and solution conditions. In this work, we investigate the surface coverage of the droplets and the correlation between the base area of the droplets and of the bare zone surrounding the droplets for various flow and solution conditions during the solvent exchange. The surface coverage increases with the increase in the flow rate, channel height and the oil concentration, and reaches a plateau between 35% and 50%. The spatial correlation is analysed with the help of the radial distribution function g(r) and a Voronoi tessellation. When the surface coverage reaches [similar]25-30%, the number density of the droplets starts to drop, reflecting the mutual interaction and merging of the droplets. With further decrease in the droplet spacing and increase in surface coverage, the Voronoi analysis shows that the base area of the droplets increases linearly with the area size of the depleted zone. The collective interaction in the growth of surface nanodroplets is universal, independent of the specific conditions that control the droplet growth.

Solvent exchange is a simple solution-based process to produce surface nanodroplets over a large area. The final size of the droplets is determined by both the flow and solution conditions for a given substrate. In this work, we investigate the growth dynamics of surface nanodroplets during solvent exchange by using total internal reflection fluorescence microscopy (TIRF). The results show that during the solvent exchange, the formation of surface nanodroplets advanced on the surface in the direction of the flow. The time for the number density and surface coverage of the droplets to reach their respective plateau values is determined by the flow rate. From the observed evolution of the droplet volume and of the size of individual growing droplets, we are able to determine that the growth time of the droplets scales with the Peclet number Pe with a power law ∝Pe-1/2. This is consistent with Taylor-Aris dispersion, shedding light on the diffusive growth dynamics during the solvent exchange. Further, the spatial rearrangement of the droplets during coalescence demonstrates a preference in position shift based on size inequality, namely, the coalesced droplet resides closer to the larger of the two parent droplets. These findings provide a valuable insight toward controlling droplet size and spatial distribution.

The controlled dissolution of microdroplets on a supporting substrate is an effective approach that can be used to tune the assembled microstructure of basic units suspended within the droplet. In this work, we studied the self-assembly of two-dimensional graphene oxide (GO) nanosheets driven by the dissolution of a microdroplet situated at the interface between a solid substrate and the surrounding liquid phase. We found that although uniform microstructures form at the liquid-liquid interface of the droplets, the contact between the droplet and the substrate can give rise to a variety of different morphologies near the base of the droplet. In particular, pinning effects at the boundary of the dissolving droplet on the substrate lead to non-spherical GO assemblies. The results in this work demonstrate the possibility that tailored three-dimensional architectures of nanosheets assembled in a dissolving droplet may be achieved through control of the wetting properties of the droplet on the supporting substrate.

The solvent exchange procedure is an often-used protocol to produce surface nanobubbles. In this procedure, the substrate is exposed to a good solvent for gas which is then mixed and rinsed with a poor solvent for gas and the nanobubbles form on the solid-liquid interface. Here we study the effects of temperatures of the substrate and the first solvent on nanobubble formation. Atomic force microscopy with temperature control was used to examine the formation of nanobubbles at temperatures between 37 °C and 54 °C. It was found that the probability of nanobubble formation was larger on substrates at higher temperatures. Moreover, on warmer substrates we found nanobubbles with lateral extensions up to 8 μm. A morphologic analysis shows that all nanobubbles, including giant nanobubbles, have a similar aspect ratio, independent of the substrate temperature, and that this aspect ratio corresponds to a contact angle between 13° and 22° (on the gas side), much smaller than the macroscopic counterparts. We finally discuss the implications of our results for various theories on nanobubble stability.

The behaviour of nanobubbles and nanodroplets at solid–liquid interfaces in an acoustic field is of interest in terms of both fundamental research and the various applications of nanofluids coupled with ultrasound. Herein, we show by in situatomic force microscopy imaging that nanobubbles experienced growthvia rectified gas diffusion yet did not nucleate cavitation. Nanodroplets were remarkably immobile after a period of initial mobility in the sound field. The stability of the interfacial nanofluids towards ultrasound may be attributed to pinning on the three-phase contact line.

We have studied how cellulose nanocrystals (CNC) self-assemble into liquid crystalline phases in shrinking, isolated droplets. By adjusting the water dissolution rate of an aqueous CNC droplet immersed in a binary toluene-ethanol mixture we can control the final morphology of the consolidated microbead. At low ethanol concentration in the surrounding fluid dense microbeads of spherical morphology are produced while collapsed core-shell particles are obtained at high ethanol concentration. Polarized light microscopy was used to follow the spatial evolution and coalescence of birefringent spheroids during droplet shrinkage. Electron microscopy reveals the resultant nematic microstructure. This method of confined CNC assembly provides thus the possibility to prepare ordered microbeads, which can be useful as templates or for their optical properties.

The dissolution dynamics of microscopic oil droplets (less than 1 μm in height, i.e. nanodroplets) on a hydrophobilized silicon surface in water was experimentally studied. The lateral diameter was monitored using confocal microscopy, whereas the contact angle was measured by (disruptive) droplet polymerisation of the droplet. In general, we observed the droplets to dissolve in a mixed mode, i.e., neither in the constant contact angle mode nor in the constant contact radius mode. This means that both the lateral diameter and the contact angle of the nanodroplets decrease during the dissolution process. On average, the dissolution rate is faster for droplets with larger initial size. Droplets with the same initial size can, however, possess different dissolution rates. We ascribe the non-universal dissolution rates to chemical and geometric surface heterogeneities (that lead to contact line pinning) and cooperative effects from the mass exchange among neighbouring droplets.

Nano- and micro-scale lenses have a range of potential applications, such as in antireflective layers in photovoltaic or light emission devices, and in super resolution imaging in the near field modes. One of the protocols to mass produce polymeric microlenses is through the polymerization of microdroplets of a monomer precursor that are produced at solid–liquid interfaces by a solvent exchange technique. In this work, we have advanced this protocol by using surfactants. A cationic surfactant was added to the liquid phase for the control over the formation and morphology of polymerisable microdroplets and their resultant microlenses (i.e. the polymerized microdroplets). The results demonstrate that the surfactant could enable the production of polymerizable microdroplets on hydrophilic substrates by the solvent exchange technique, and eliminate the restriction by the substrate wettability on the microlens fabrication. Furthermore, the size distribution and aspect ratio of microlenses could be tuned by the surfactant concentration.

We study the size and spatial distribution of surface nanobubbles formed by the solvent exchange method to gain insight into the mechanism of their formation. The analysis of Atomic Force Microscopy (AFM) images of nanobubbles formed on a hydrophobic surface reveals that the nanobubbles are not randomly located, which we attribute to the role of the history of nucleation during the formation. Moreover, the size of each nanobubble is found to be strongly correlated with the area of the bubble-depleted zone around it. The precise correlation suggests that the nanobubbles grow by diffusion of the gas from the bulk rather than by diffusion of the gas adsorbed on the surface. Lastly, the size distribution of the nanobubbles is found to be well described by a log-normal distribution.

Controlling of the morphology and assembly of graphene oxide (GO) is important in the structure design of carbon materials using GO sheets as building blocks. In this work, we have studied GO assembling driven by the dissolution of a droplet immersed in a surrounding liquid phase. The as-assembled GO structures were highly crumpled with exotic morphology, which we refer to as GO snowballs. The detailed structure of GO snowballs was closely related to the dissolution dynamics of the droplet, which could be adjusted by the composition of the surrounding liquid.

Nanodroplets can be conveniently produced by the established protocol, called the solvent exchange. In this work, the transient nanodroplets were converted to permanent polymeric nanolenses by forming nanodroplets of monomers followed by in situ photopolymerization. This method could produce nanolenses with desired single or multiple components over a large area on both planar and non-planar surfaces. The morphology (average size and height/lateral size ratio) and the components of nanolenses could be controlled by the characteristics of the nanodroplets.

Solvent evaporation is found to significantly affect the morphology and assembly of chemically converted graphene drop cast on certain solid substrates. On negatively charged substrates, drying could induce the flattening and self-assembly of a single layer of CCG in an edge-to-edge manner. A mechanism is proposed to explain these phenomena.

We present results focusing on whether gas bubbles are stable at all length scales at liquid/solid surfaces. Tapping mode atomic force microscopy was used to observe nanoscale bubbles of air or hydrogen produced by two methods on hydrophilic and hydrophobic solid surfaces. The observed nanobubbles of air or hydrogen always have curvature radii of less than 2.0 μm and heights of less than 100 nm, suggesting the possible instability of these nanobubbles beyond these length scales. This is further supported by the observation of blank circular areas on the electrode surface, which are interpreted as footprints of departed large bubbles with curvature radii equal to or above 2.0 μm from the surface.